An unusual example ofendo-stereoselectivity in the ligand exchange reactions of rhodium(i)diethylene derivatives withpara-semiquinoid ligands

Autor:	D. V. Zverev, V. A. Nikanorov, S. G. Novikov, S. V. Sergeev, Pavel V. Petrovskii
Rok vydání:	1996
Předmět:	Steric effects chemistry.chemical_classification Double bond Chemistry Ligand Stereochemistry chemistry.chemical_element General Chemistry Medicinal chemistry Rhodium Metal chemistry.chemical_compound visual_art Atom visual_art.visual_art_medium Stereoselectivity Benzene
Zdroj:	Russian Chemical Bulletin. 45:2203-2206
ISSN:	1573-9171 1066-5285
DOI:	10.1007/bf01430741
Popis:	The ligand exchange reactions of [(C2H4)2Rh(acac)] in benzene and [(C2H4)2RhCl]2 in CH2Cl2 with 4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one occur with 100%exo-stereoselectivity. The similar process with 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-4,6-dioxocyclohexylidene)-2,5-cyclohexadiene (trienedione) is strictlyexo-stereospecific only if [(C2H4)2Rh(acac)] in benzene is used, while in the case of [(C2H4)2RhCl]2 in CH2Cl2, it proceeds with anendo-stereoselectivity of 43%. An explanation for these facts has been suggested that assumes that the metal atom initially attacks the central double bond in the trienedione, which is removed from the area of main steric hindrance. The subsequent metallotropic rearrangement of the resulting ethylene-triene intermediate gives rise to the final η4-coordinated π-diene structures.
Databáze:	OpenAIRE
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